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Journal of Food Engineering 100 (2010) 225–231

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Journal of Food Engineering


journal homepage: www.elsevier.com/locate/jfoodeng

Influence of salt concentration on the salting kinetics of cod loin


(Gadus morhua) during brine salting
Minh Van Nguyen a,*, Sigurjon Arason a,b, Kristin Anna Thorarinsdottir b, Gudjon Thorkelsson a,b,
Agusta Gudmundsdóttir a
a
Faculty of Food Science and Nutrition, University of Iceland, Dunhagi 5, 107 Reykjavı ´k, Iceland
b ´ nlandsleid 12, IS-113 Reykjavı
Matı́s ohf./Icelandic Food and Biotech R&D, Vı ´k, Iceland

a r t i c l e i n f o a b s t r a c t

Article history: The influence of different salt concentrations of 6%, 15%, 18% and 24% (w/w) on mass transfer of water
Received 15 December 2009 and salt during brine salting of cod loins was studied. An increase in salt concentration accelerated water
Received in revised form 26 March 2010 exudation and salt diffusion in the cod loins. Weight gain of the cod loins increased with decreasing salt
Accepted 2 April 2010
concentration and the cod loins in the 6% brine had the highest process yield. The salting kinetic param-
Available online 9 April 2010
eter values for total and water weight changes decreased with increasing salt concentration. Inversely,
higher salting kinetic parameter values for salt weight changes were observed for higher brine concen-
Keywords:
trations. The samples brined at 18% and 24% had identical effective diffusion coefficients and the highest
Cod
Brine salting
effective diffusion value was found in the cod loins brined at 15%.
Mass transfer Ó 2010 Elsevier Ltd. All rights reserved.
Salt diffusion
Water holding capacity

1. Introduction (Andrés et al., 2002; Barat et al., 2003). Diffusion is the most impor-
tant one (Barat et al., 2002; Wang et al., 2000), resulting from
Salting is one of the oldest methods for fish preservation. It is differences in concentration and osmotic pressures between the
based on the penetration of salt into the fish muscle. Nowadays, muscle and the salting agent (Raoult-Wack, 1994; Yao and Le
salting is considered to give specific sensory characteristics to Maguer, 1996) and from concentration gradients within the
the final product (Andrés et al., 2005; Boudhrioua et al., 2009; muscle (Erikson et al., 2004). The chemical fluxes are also influ-
Esaiassen et al., 2004). Salting is performed either by dry, brine, enced by pressure gradients within the muscle which change
or injection salting or a combination of these methods. Dry salting during salting due to denaturation/aggregation of the muscle
has been the most commonly used methods by the industry. Dry proteins (Jittinandana et al., 2002; Sannaveerappa et al., 2004;
salting is the traditional salt-curing technique used during process- Thorarinsdottir et al., 2004).
ing of salted fish in many countries (Gallart-Jornet et al., 2007a; Many studies have dealt with the salting kinetics of fish (Andrés
Lauritzsen et al., 1999). In recent years, brine salting has become et al., 2002; Barat et al., 2003; Boudhrioua et al., 2009; Fuentes
popular for processing salted cod as a pre-salting step, followed et al., 2007, 2008; Gallart-Jornet et al., 2007a,b; Wang et al.,
by dry salting (Thorarinsdottir et al., 2004). Brine salting has 2000). The brine concentration and temperature are the main
several advantages over dry salting including shorter processing factors affecting the rate of water and salt diffusion (Bellagha
time due to higher salt uptake and higher weight yields due to a et al., 2007; Boudhrioua et al., 2009; Poernomo et al., 1992). Salting
better control over the rate of salt uptake and water loss in the rates are also influenced by a number of intrinsic factors in the
muscle (Andrés et al., 2005; Beraquet et al., 1983; Thorarinsdottir muscle, such as fat content, rigor state and temperature (Birkeland
et al., 2004). It can also improve colour and appearance of salted et al., 2004; Gallart-Jornet et al., 2007a; Jittinandana et al., 2002);
cod products when applied at levels <20% (Thorarinsdottir et al., the contact area, initial weight and presence of skin in the fish fil-
2004). lets (Fuentes et al., 2007, 2008).
Salt and water transfer in fish muscle during the salting process The aim of this study was investigate the influence of different
is complicated and depends on various mass transfer mechanisms salt concentrations (6%, 15%, 18% and 24% (w/w)) on the salting
kinetics and weight of skinless cod loins during brining for up to
* Corresponding author. Tel.: +354 4225000; fax: +354 4225001. 48 h. The brine concentration was kept nearly constant by increas-
E-mail address: mvn2@hi.is (M.V. Nguyen). ing the ratio of brine to fish.

0260-8774/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2010.04.003
226 M.V. Nguyen et al. / Journal of Food Engineering 100 (2010) 225–231

Nomenclature

DMot total weight changes of cod loin in the bringing process vNaCl
0 ; vNaCl
t salt weight fractions in the samples at the beginning
DMw water weight changes of cod loin in the brining process (0) and at the sampling time (t)
t
ZNaCl salt concentration in the cod muscle liquid phase
DMNaCl salt weight changes of cod loin in the brining process
t vw water weight fraction of the samples
Mo0 ; Mot sample weight fractions at the beginning (0) and at the vNaCl salt weight fraction of the samples
sampling time (t)
vw0 ; vwt water weight fractions in the samples at the beginning
(0) and at the sampling time (t)

2. Materials and methods 2.3. Water holding capacity (WHC)

2.1. Raw material Water holding capacity was determined by a centrifugation


method (Akse et al., 1993; Eide et al., 1982). The fish meat was
Cod (Gadus morhua) was caught in April by a bottom trawl coarsely minced in a Braun Mixer (Type 4262, Germany) for 10–
on the Southwest coast of Iceland by a commercial fishing trawler. 15 s and 2 g of the sample were weighed in the glass. Samples were
The average weight of the gutted fish was 2.8 ± 0.2 kg. On board, centrifuged at 210g for 5 min at 4 °C (Heraeus Biofuge Stratos
the fish was gutted and stored for 2 days. The fish was filleted, Reconditioned 75005289 R, Rotor 3335, DJB Labcare Limited, Eng-
skinned and the cod loins were cut from the fillets on arrival at land). Centrifugation loss of water was calculated as the difference
the HB Grandi Company, in Reykjavik, Iceland. The mean core tem- in weight before and after centrifugation. The water holding capac-
perature of the cod loins was then 0 °C. The loins were stored in ice ity (expressed as percent WHC) was calculated as the ratio of
mat and transported to the Matis laboratory in Reykjavik where remaining water compared to the water content in the sample be-
the experiments were carried out. fore centrifugation.
Industrial salt (Bahamas) taken from the same sack was used for
preparing the brine throughout the experiments. Although the salt 2.4. Chemical determinations
was not analysed in this study, typical chemical composition of the
salt is shown in Table 1. Water content was determined according to ISO 6496 (1999).
Salt content of all the samples was determined by titration accord-
2.2. Brining and sampling ing to AOAC (1995). Salt concentration referred to cod muscle li-
quid phase (zNaCl) was estimated from determination of weight
The cod loins were cut into small slices (100–120 g) with the fractions of water (vw) and sodium chloride (vNaCl). The zNaCl con-
dimensions of length 9–10 cm, width 3.5–4 cm and height 2.5– tent was calculated by Eq. (1) (Barat et al., 2002):
2.7 cm. The slices were individually weighed and tagged. The slices  
were collected randomly and salted by immersing them in brine vNaCl
Z NaCl ¼  100 ð%Þ ð1Þ
with four different salt (NaCl) concentrations (6%, 15%, 18% and vNaCl þ vw
24% (w/w)) at a ratio of 11:1 (brine:fish) to avoid significant dilu-
tion of the medium by water removal. Samples for each sampling
point were brined in one closed plastic container. In order to max- 2.5. Mass changes in weight, salt and water
imize the diffusive surface, the slices were arranged on the plastic
grid. The salting process was carried out at 2 °C for 48 h. Ordinary, The total weight changes ðDM ot Þ, water weight changes ðDM w t Þ

industrial salt (Bahamas) and distilled water were used to make and salt weight changes ðDM NaCl t Þ were calculated by means of
the brine. To calculate the yield during salting, slice-weight Eqs. (2)–(4) (Barat et al., 2002; Gallart-Jornet et al., 2007a,b):
(n = 5) was recorded after drainage for 2–3 min on a grid at differ-  o 
ent sampling time (0, 2, 4, 6, 8, 10, 14, 24, 28, 34 and 48 h). At each M t  Mo0
DMot ¼ o  100 ð%Þ ð2Þ
sampling point, three slices of cod loin were chosen randomly and M
 o 0w 
determined separately for water holding capacity, salt content, and Mt  vt  Mo0  vw
water content. DM w
t ¼ o
0
 100 ð%Þ ð3Þ
M0
 o NaCl 
M t  vt  M o0  vNaCl
DMNaCl
t ¼ o
0
 100 ð%Þ ð4Þ
Table 1
M0
Chemical composition of the salt from Bahamas (Morton Bahamas Limited, 2009).

Chemical composition Content 2.6. Mass transfer kinetics


Water (%) 2.30
NaCl (%) 97.23 In order to elucidate the mass transfer phenomena that take
CaCl2 (ppm) 0.00 place during the brining process, a mathematical model for the
CaSO4 (ppm) 4.38
MgSO4 (ppm) 303
weight changes was fitted to the experimental data. In this model,
MgCl2 (ppm) 450 weight changes were considered to be dependent on the square
Na2SO4 (ppm) 0.00 root of time and a pseudo-diffusional transportation was assumed
Matter insoluble in water (%) 0.01 (Barat et al., 2002; Fuentes et al., 2008; Gallart-Jornet et al., 2007a).
Iron (mg/kg) 1.70–2.69
Weight changes during the brining process were calculated accord-
Copper (mg/kg) <0.01
ing to Eq. (5) (Andrés et al., 2002).
M.V. Nguyen et al. / Journal of Food Engineering 100 (2010) 225–231 227

DM it ¼ 1 þ k1 þ k2  t0:5 ð5Þ 3. Results

3.1. Mass transfer


DM  ti includes total weight changes ðDMot Þ, water weight changes
ðDM wt Þ and salt weight changes ðDM t
NaCl
Þ during the brining process
3.1.1. Mass balance applied to the cod loins during brining
as a function of the square root of time. The independent term (k1)
The main components transferred between the fish and its sur-
describes what happens in the samples at the beginning of the
roundings during brining were water and salt (Andrés et al., 2002;
brining process. It is mainly affected by the salt concentration,
Duerr and Dyer, 1952), as observed when the DM ot of the four
water activity gradients and to some extent the pressure gradients
experimental groups were plotted against the sum of the DM w
(Andrés et al., 2002; Barat et al., 2003). The slope term (k2) is t
and DM NaCl (Fig. 1). Generally, the plotted points located slightly
related to the kinetics of the diffusion mechanisms, in term of t
above the diagonal indicated loss of other sample components
process yield, and it depends on the brine concentration (Andrés
such as tiny cod fragments and soluble muscle components like
et al., 2002).
proteins (Barat et al., 2004, 2006; Martı́nez-Alvarez and Gómez-
Guillén, 2005). The concentration of the brine did not seem to
2.7. Salt equilibrium equation
influence the deviations as might have been expected, i.e. that
higher losses would be obtained at levels were the protein solubil-
When regarding the equilibrium stage of the brining process, it
ity is high (Stefansson and Hultin, 1994).
was assumed that the salt concentration in the muscle liquid
phase ðZ NaCl
e Þ would be equal to that of the brine solution ðyNaCl
e Þ
(Barat et al., 2004). The Z NaCl
e and yNaCl
e values could be obtained
3.1.2. Mass changes in weight, salt and water
by taking into account the initial cod loin/brine solution ratio
The total weight changes ðDM ot Þ of the cod loins during brining
ðMCL BS
0 =M 0 Þ and the initial of both salt and water weight fractions
were significantly affected by the brine concentration (p < 0.001)
in the cod loin (vNaCl
0 and vw 0 , respectively) and in the brine solu-
NaCl w and brining time (p < 0.001). Increase in weight was observed at
tion (y0 and y0 , respectively). The values previously mentioned
brine concentrations of 6%, 15% and 18% (w/w) throughout the
were calculated by using a mass balance (Eq. (6)) (Barat et al.,
brining time (Fig. 2), whereas the samples brined at 24% decreased
2004, 2006).
in weight during the first 14 h but after that the weight tended to
M CL increase again.
0
MBS
 vNaCl
0 þ yNaCl
0
Z NaCl
e ¼ yNaCl
e ¼ 0
 100 ð%Þ ð6Þ
MCL
0
M BS
 ðvw
0 þ v0
NaCl
Þ þ ðyw NaCl
0 þ y0 Þ
0 30

2.8. Salt effective diffusion coefficient (De) 25


NaCI

20
The changes in ZNaCl values (liquid phase salt weight fraction of
Mt

cod loin) and yNaCl values (salt weight fraction of brine solution) 15 6%
during brining were used to determine the effective diffusion coef-
w
Mt

ficient (De) of the cod loin samples by using the integrated solution 10 15%
of Fick’s equation for semi-infinite slabs and short brining time (Eq. 18%
(7)) (Crank, 1975). Y NaCl
t was the reduced driving force between the 5
cod loin liquid phase and the brine solution; l was the haft-thick- 24%
ness of cod loin (ffi1.3) (Gallart-Jornet et al., 2007a); De (m2/s) 0
was the effective diffusivity and the independent term (K) was in- -5 0 5 10 15 20 25 30
-5 o
cluded in the Eq. (7) and would allow for correction of any effect of Mt
salt concentration, water activity gradients and some extent of
pressure gradients or any other mass transfer phenomena that oc- Fig. 1. Mass balance of samples brined in brine concentration of d, 6%; N, 15%; ,
18%; j, 24% (w/w), at the different sampling points.
cur at the very beginning of the brining process (Barat et al., 2002,
2004).

" #  0:5
Z NaCl  yNaCl De  t 35 6% 15% 18% 24%
1  Y NaCl
t ¼1 t t
¼2 2
þK ð7Þ
Z NaCl
0  Z NaCl
e pl 30
25
The 1  Y NaCl
t values were obtained by adjusting the experimental
data to the Eq. (7). 20
15
2.9. Statistical analysis
o
Mt

10
The obtained data sets were analysed by stepwise multiple
5
regressions to study the relationship between processing variables
(brining time and brine concentration) and dependent variables 0
(total, water and salt weight changes). The significant differences
-5 0 4 8 12 16 20 24 28 32 36 40 44 48
between mean values of coefficients of variance were evaluated
using one-way ANOVA. The kinetic parameters were analysed with -10
Brining time (hours)
a simple linear regression (least-squares) (Sigmastat 3.5 – Jandel
Scientific Software, Ontario, Canada). Differences between samples Fig. 2. Total weight changes of cod loins during brining at different brine
were considered to be significant at p < 0.05. concentrations (d, 6%; N, 15%; , 18% and j, 24% (w/w)).
228 M.V. Nguyen et al. / Journal of Food Engineering 100 (2010) 225–231

35 6% 15% 18% 24% 100


30 96
25 92
20 88

WHC (%)
15 84
10 80
w
Mt

5 76
0 72
-5 0 4 8 12 16 20 24 28 32 36 40 44 48 68
-10 64 6% 15% 18% 24%
-15 60
-20 0 4 8 12 16 20 24 28 32 36 40 44 48
Brining time (hours)
Brining time (hours)
Fig. 3A. Water weight changes of cod loins during brining as function of brine
concentration (d, 6%; N, 15%; , 18% and j, 24% (w/w)). Fig. 4A. Changes in water holding capacity in cod loins during brine salting as
functions of brine concentration and time (d, 6%; N, 15%; , 18% and j, 24% (w/w)).

30
20 6% 15% 18% 24% 6%
25 Salting-in Salting-out
15%
18
20 18%
16 24%
14 15
τ (%)

12 10
Mt NaCI

10
ΔΜ ω

5
8
0
6
-5 0 2 4 6 8 10 12 14 16
4
2 -10
0 -15
0 4 8 12 16 20 24 28 32 36 40 44 48
-20
Brining time (hours) zNaCl (%)
Fig. 3B. Salt weight changes in cod loins as functions of brining time and brine
Fig. 4B. Relationship between water weight changes and salt content in the liquid
concentration (d, 6%; N, 15%; , 18% and j, 24% (w/w)).
phase of cod loins during brining at different brine concentrations (d, 6%; N, 15%; ,
18% and j, 24% (w/w)).

The salt weight changes ðDM NaCl t Þ increased with increasing 3.3. Mass transfer kinetics and salt effective diffusion coefficient (De)
brine concentration whereas the water weight changes ðDM w t Þ de-
creased (p < 0.001) (Figs. 3A and 3B). The samples brined at 6% and
3.3.1. Salting kinetic parameters
15% (w/w) gained water throughout the brining process. On the
The total weight changes of cod loins during the brining process
other hand, the samples brined at 18% (w/w) lost water during
as a function of the square root of time and the equation coeffi-
the first 24 h of brining, followed by water gain after an additional
cients, period of time fitted and the fitting correlation factors are
24 h. The highest water loss was observed in the samples brined at
shown in Fig. 5 and Table 2, respectively. The k1 and k2 values
24% (w/w) throughout the brining process.
for total and water weight changes (DM ot and DM w t ) gradually de-
creased with increased brine concentration. Conversely, the k1
and k2 values for salt weight changes ðDM NaCl Þ gradually increased
3.2. Changes in water holding capacity (WHC) during brine salting t
with increased brine concentration (Table 2).
The WHC of all samples brined at all four brine concentrations
of 6%, 15%, 18% and 24% (w/w) increased significantly (p < 0.001) 3.3.2. Salt effective diffusion coefficient (De)
(from 86.8% to 99.3–99.6%) after brining for 2 h (Fig. 4A). After that, The 1  Y NaCl
t values plotted versus t0.5 and the De and K values
the WHC was rather stable throughout the brining process for sam- are shown in Fig. 6 and Table 3, respectively. The highest De value
ples brined at 6%, 15% and 18% (w/w). However, there was a signif- was observed in the samples brined in the brine concentration of
icant drop (p < 0.001) in WHC of the samples brined at 24% (w/w) 15% (w/w). The lowest De values were found in the samples brined
observed near the zNaCl value of 15%, after brining for 14 h (data not in the brine concentration of 18% and 24% (w/w). The De value in
shown). samples brined at 6% brine concentration was slightly higher than
The DM w NaCl those of 18% and 24% (Table 3).
t values plotted against z are shown in Fig. 4B. The
samples brined at 6% and 15% gained water while the samples
brined at 18% were similar to the raw muscle and remained like 3.3.3. Salt equilibrium
that during the brining process. Inversely, water loss was observed Comparison of the experimental ZNaCl values analysed and the-
in the samples brined at 24% (w/w). oretical values calculated by means of Eq. (6) showed that none of
M.V. Nguyen et al. / Journal of Food Engineering 100 (2010) 225–231 229

35 6% 15% 18% 24% the groups reached salt equilibrium at the end of the brining pro-
cess. The experimental values for samples brined in concentration
30 of 6%, 15%, 18% and 24% (w/w) at 48 h were 4.70respectively,
25 whereas the theoretical values were 5.6122.37%, respectively.

20
4. Discussion
o

15
Mt

10 4.1. Mass transfer and water holding capacity


5
The observed pattern of weight and chemical changes in this
0 study was in agreement with previous studies (Barat et al., 2002,
-5 0 1 2 3 4 5 6 7 8 2003; Gallart-Jornet et al., 2007a; Schmidt et al., 2008; Thorarins-
dottir et al., 2004). Samples brined at 6% (w/w) presented the high-
-10 t0.5 (h0.5) est water uptake and a strong water holding capacity possibly due
salting-in effects on proteins. This is especially true during the
Fig. 5. Plot of total weight changes ðDM ot Þ of cod loins versus the square root of time
early stages of the brining process. However, at a higher salt con-
t0.5 (h0.5) (, 6%; N, 15%; , 18% and j, 24% (w/w)).
centration (>1 M), protein aggregation (i.e. salting-out process)
lead to less space for water, resulting in decreased water content
and lower WHC (Fennema, 1990; Gallart-Jornet et al., 2007b; Offer
Table 2
and Trinick, 1983; Thorarinsdottir et al., 2004), as observed for the
Kinetic parameters for total, water and salt weight changes ðDM ot ; DM w NaCl
t and DM t )
fitted to Eq. (5) (k1 and k2), and fitting correlation factors (p < 0.05). 24% group. The degree of protein aggregation in the 24% brine was
probably higher than that of other brine concentrations, leading to
Brine concentration (%) k1 k2 R2
a higher water loss from the muscle (Akse et al., 1993; Fuentes
DM ot 6 2.963 3.653 0.953 et al., 2008; Gallart-Jornet et al., 2007a,b). However, the total
15 1.683 2.633 0.941
weight changes of the samples brined at 24% (w/w) tended to in-
18 0.039 1.908 0.889
24 1.089 0.075 0.022
crease again after brining for 14 h. This may be due to the concen-
tration gradients within the fish muscle during the brining process
DM w
t
6 2.291 3.354 0.938
15 0.467 1.107 0.800
(Erikson et al., 2004). The salt concentration of the inner parts of
18 1.819 0.230 0.077 the fish muscle was probably still below the salting-out level
24 3.681 2.026 0.805 (>1 M). Therefore, the muscle may have started to swell, resulting
DM NaCl 6 0.635 0.750 0.895 in weight gain.
t
15 1.166 1.888 0.951 At the same zNaCl value, the added water to the samples brined
18 2.322 2.104 0.924 at 6% was higher than that of the samples brined at 15%, due to
24 2.799 2.269 0.911
stronger swelling-in of myofibrils in muscle. In samples brined
at 15%, there was a mixed effect of salt on muscle proteins and
microstructure. The surface layer lost water due to salting-out
effects, whereas the inner parts gained water due to salting-in
1 effects.
0.9 The obtained rate of weight changes in the cod loin samples of
this study was higher than that of previous studies (Barat et al.,
0.8
2002, 2003; Gallart-Jornet et al., 2007a; Thorarinsdottir et al.,
0.7 2004). This may be due to the higher brine:fish ratio used in
0.6 this study, resulting in higher component activity- and pressures
1-YNaCl

0.5 6% gradients between the muscle and brine and within the muscle.
0.4 In addition, the use of skinless cod loins and different sample
15% arrangements seem to have maximized the diffusive surface of
0.3
the samples leading to an increased rate of salt and water diffusion.
0.2 18%
0.1 24% 4.2. Mass transfer kinetics and salt effective diffusion coefficient (De)
0
0 1 2 3 4 5 6 7 8 4.2.1. Salting kinetic parameters
t0.5 (h0.5) The mass transfer of NaCl was driven by a concentration gradi-
ent between the muscle and brine and within the muscle as indi-
Fig. 6. Reduced driving force (1-YNaCl) versus t0.5 (d, 6%; N, 15%; , 18% and j, 24% cated by the increasing k1 and k2 values for DM NaCl t with
(w/w)). increasing brine concentration (Andrés et al., 2002; Barat et al.,
2003; Gallart-Jornet et al., 2007a,b). Salt uptake was observed for
all groups in subsequent stages of the brining process mainly due
to the differences in concentration gradients between the muscle
Table 3
and brine and within the muscle. However, the k2 value was higher
De and K values obtained by fitting the Eq. (7) to the experimental data.
at higher brine concentration. It may be due to the stronger
Brine concentration (%) De (m2/s) (1010) K R2 magnitude of the driving forces at higher brine concentration com-
6 4.188 0.199 0.800 pared to lower concentrations. In addition, salting-out and shrink-
15 5.449 0.141 0.904 age of the muscle fibers resulted in larger extra-cellular spaces/
18 4.001 0.262 0.912
channels (Ockerman et al., 2003), favouring higher diffusion rates
24 4.009 0.214 0.945
of salt.
230 M.V. Nguyen et al. / Journal of Food Engineering 100 (2010) 225–231

The highest rates in water uptake/loss were obtained at brine Acknowledgements


concentrations of 6% and 24%, respectively. The k1 values for
DMw t of the samples brined at 6% and 15% were positive, but nega- We would like to acknowledge the financial support from the
tive values were obtained for the samples brined at 18% and 24% United Nations University-Fisheries Training Programme, Matis
(Table 2). The results for 6% and 15% indicate that already at the (Icelandic Food and Biotech R&D) and Nordic Innovation Centre
early stages of the brining process, pressure gradients become a Fund (project no. 04252).
stronger force than water activity gradients due to the salt induced
swelling of the myofibrils (Akse et al., 1993; Barat et al., 2002;
Xiong, 2005). During salting, the magnitude of pressure gradients References
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